AU694961B2

AU694961B2 - Anhydrous cosmetic compositions containing TiO2 nanopigments and flexible hollow microspheres

Info

Publication number: AU694961B2
Application number: AU61296/96A
Authority: AU
Inventors: Laure Guillemot; Isabelle Hansenne; Delphine Ribery
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 1995-07-13
Filing date: 1996-06-14
Publication date: 1998-08-06
Anticipated expiration: 2016-06-14
Also published as: CN1195979A; CA2224481C; FR2736543A1; EP0755670B1; KR19990028949A; EP0755670A1; WO1997002806A1; DE69600020T2; CA2224481A1; BR9609602A; AU6129696A; FR2736543B1; AR002789A1; ES2105914T3; KR100275022B1; ATE153238T1; DE69600020D1; JPH11507392A; MX9800420A; JP3242667B2

Description

AX4mi,3 par: DPI L OREAL +33 1 47 SG 73 88 Ic 12,18V1/9 426 A4 NORM Pff: 3/49 ANMYRQUS; COSME1TIC COMPOI'sTI1ONS CONTAININJG TiO7 NANOPIGKENTS AND DEFO".AHLF. HOLLOW

MICROSJJIFRES

The present invention Tr1ltC-S to a novel anhydrous compcwoiLio i or Lopical u~se which is intonded more particularly for thco, phot.oprotection of the skin and/or the hair against ultra-vjol0.d. radiation, as well as to its use iii the cosmetici fiold. This composition contains, in a nosrnctix vn'hcln COILsiSting Of a fatty phase, at least. crte Litaniwri oxide- nanopigment and dcformablc hol~low microphere- of ali expandcd copolyme X of -vinylidene chloride and acryloni tril'. or of vinylidene chlori.do, aCryj.oriit.Vi2.- and methacrylate.

It krjcwxI Lhat: liqhlt radiation with 1s wavalcngthr, oi Ist.wer± 280) nxii and 100 Txm pQormit,-A tanining of the human epidermL. aid Lhhat light rays with wavolengt1i, between 280 rn zinrt .320 xwt, known as IN-B rays, cause skin burns ai-ad eryLheina which may be harxmful to the iiidLural development' of the tan; this UV-B radiationi :-,hould thus be screened out.

waveleng ths of bten320 -mand 400 nwithcas e.IIS'.tve ki 07 o L~irlWhch ":conti.nually 0.x Posed to ;olr rdiaion U-A ayscau:Einparticular a I lo:s of elastic:;L t y of the skin and h appearance of

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FOlX 6-is Par: DPI L OREOL +33 1. 47 SG 73 88 la 12/01/98 14:20 M4 tORfl Pg: 4/419 wrinkles, 3.eadiny to prematuro. angetng. They promote triggering of tc, erythema). rv~eacin or amplify this reaction ii cei:Lain individual,~ atid may even be the cause of photuxic or photoal Irrcic reactions. It is thus desirable altso to screcn out TrV-A radiation.

Various types of ounIcresn exist on the xnarkat to vureeL out tJV.,A andI CV-k radiation: inorgranic pigments~ and otyanic screeni.ng aqtriLvi These screening agents must be! able to absorb or block harmful solar rays while at thfm n-ajne time reumanng harmless to the user, Thus, many orgartic e:unscreens capablc of relatively selectivc.1.y 71b,,torbing harmful UV rays have been proposed to' datc-~ in the cosmetics field. Hiownver, is for various reas~onrs, these scTreenincg agents are riot entirely satmn Wim-o.ry.

Aco:t Ii iigty, it is iricrE-,-tingly sought to avoid the use cd, thcr;oe orqaniL' screening agcntr, by favouring thoe m of inorganic piqmcnta, which also act as sunsrceens, mainly by diL~uuizi/reflection of the INV rays, whilc aL Llie same time aftor-ding greater safety for the user.

in thi.: rcespoc.t, the irixganic pigment most commtonly used Lo date is nanopi qncnt -grade titanium oxido, whonse scrteening propc(!Y.LieS: are well kno-'a.

Howv~Hit is aijj~c, well known that, on account of itsL, hydrohicnuriO tends to be readily elimi.m2Lc.(d by water duri.Tr bat-hinc.or FrP'iY/RX NO 91821

A",

Pa:DP14 1OREAL, +33 1 47 SG 7--4 FAX 6r~iis par: DPI L OHkAL 1 ~E 73 88 le 12~81~'98 ii:2O fl4 NORfl Pg Ss~19 FAX 6mis par: DPI L 01ML +JS 1 4? S6 73 88 le 12/01/98 14:20 'A4 MORM P9: S/49 showering, for cxaxnplc, thereby Tr:uudriq the effectiveness of~ the compoition cicontair ng it. Ini order to avoid Lhi!i drawback and to~ increase the staying power in~ water of TiO 2 it is increasiLngly sought to prepa-,re totally anhydrous-, products, in particular anhyd rnii. crcam:7- Moreovot, it is ntecossary, in ,,rde-r to obtain ouitable proftol.ion factors, to hE' able to introduce high percenttage±; of TiO,. into the ontisun compositions, in particular pcnrcentages hi hor tHian 5% by wcight.

Howcv.r):, With SUChI aon0TLJ'zIt, Of TiO,, compositions containing thesae piqrnirits ohow inrtability to light in an oxygen-free medium, which is manifested by the appearaico Of a blue coloui. This photocoloration, known as photobhluoing, is obviously not ansthctira1 ly dersirabcz.

Aricnt.ho~r pro~blem obs:ervedI with composi tions containing high C:0TILUTILTJ. of xin;iqmzicz-qrade TiO, is a whitened appearance when they are '.jpplied to the skin.

20 This phenonen.oi it; nn-t. cic-shlftfeally cderirable either.

Thus, there is currently atill a strong need to obtain anhydy.ous antisun compositions containing TiO2,f which do a.4u have, or have tci only a limited extent, the )plao t'oh ~ueing and whitening phenomena mcntioned abovc.

Thc irivn: nntion aii to sati :fy s.uch a need.

J

4 is;

II.

Thus, aftc)r considcribln rej,:(-.arch conducted

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FAX 6M'is par: DPI L OREAL +33 1 47 S6 73 88 IC 12/131/98 i412'0 A4 NORM P& 6/'49 in the photoprot.tei:tion field zncnt~ciznec above, tho Applicant has now discovered that. thn introduction of deforxnablc hollocw xirospherct. int-c, an anhydrous composition con .&nirig TiO. nio~pi qients si..ificant.y reduces the whi t.exing and UV-medizited photobluoing phenomena of the composition when Lt is applied to the skin.

This di:;covory forms the ba,.is of the present invention.- Thus, Izn ncocordaxce with one of tho subject,-; of the present iinvention, nIovVl aniklydrour, coom~etic compositionu, iii particular antisun compositions, are now proposed, c.2Mracto-rized in thatt they comprise, in a cosmectically ac.c.ptab.le vchi.o.o consisting of a fatty phase, at loast onie ti tanjiun oxidc- rianopigment and deformable hoI 2 ':ow micro..'Phe77e'.' Of an expanded copolymer of -vinylideno :1inride -and Ororitr~ o vinylidene chlCQride, acrylcanitrjIf, anrd mothacrylate.

Tha-r-E: compositio:.; arc- preterably in the form of crctm-s or niji k.i ha-ving a visco,,ity which is pufficient to ma~intain the. nanopigments stably in dispersion.

T1he coutoos:i Lions in accu):dance with the invention have- iiiany advantaqes.

Blirnt.Iy, thco photrob.Iuiiicj observed during exposure of thei< coxrpoditio: ti, o light in the absence of oxiygrn jsvcry low, or evei) iloweistent.

No xt, Uihese cops1io~also have the I I.

FAX k6m is Par: DPIr LI OREAL +*33 1 7S 3k le 12/0l4f 9iz 4Nff g 4 advantage of whi ILening oxily very sii.9htly whcn they are applied to the nln The ccitinoritions accordizq to the invention also have a high n:un protection i~ctor, on account of the fact that ucu:y high Ti0) 2 cont.exit;; may be introducod therein.

La,;tly, tho compositiono in zaccordance with the invention ZaT' Of improved stabiLlity, and the grea.-y and oticky effoot. gonerally ao!iociated with anhydrous products is aloo gre~atly reduced.

The jILQIvt*itiorx also rciates Lo the usc of these compos iiim;a; or for t-ht manufacture of, cosmetic coxnpozit.iont; for protcctinq thc sikin and/or the hair.

Ancoth- subject of tho invcrition is a cosmetic trcatmi'iit. procesr, in part.~ ~ular for the photoprotectiori ot the tkin and t.Jic haiir, which consists in apjIying an effectivtu oount of a composition wjh sthat defixird Lhove to the :Ain and the hair.

The xi..opigmnts us;ed in the compositions according to thu: invntion arcn titn;TliuMr oxIido nanopigmnt which are known pirr~u which are usually us ed in thc co.mr.-tics field and which may be treated or u.ntreate-d. ThL- f. iLanitui oxide may be- in ruti) c, ariatsee orC Imorphous frw'ni, buiE is pref.Tora]:y in rutile and/or I' anatase form The Lt.rm nriaopigments, i.s uziderstood to refer

SRA

FAX 6is. Par, DPI ~EL"+~j~is ei~~ 4 z2AtO~ ~i- FAX6rIjzf Par': IDPI L OREAL +33 147 SG 73S se iZ//,09 9 "I 4 ,:20 A4 NORM Pgi 8/49 to pigmcnts whoo cvaf lemnwitijry p.nrticle size io between 5 and 100) rim.

The trw~ttcd nanzopigi-nenLU: xmy, foz' eXample, be treated With al iiinri, silica, alimiiniuzu cmond, viilicon compounc;, nodium compounds, iron oxidles, iron esters, stear.iLc aicid or' glycerol.

More L'.rticularly, tho LL'eated nanopigmtento xmay be titaniiumn oxjdr., trrated with: s ilica and alumiia, rouch as thie product,- "Microtitnium cioxicle MT S00 SAI rid "Microtitanium dioxide MT 100 froix the company Tayca, and the products I"TioveiJ Fin", "Tiovei). "'Tioveij. MOTG"I and Tiovei. IPM"I [rom. Lhe company Tioxide, -alumina and LULLrlinium stearate, rsuch as- tbc. product is "Micro titanium di1oxi de MT 100 T" J ho the company Tayca, -alumnina and ei~iiminiun lanraLe, ,;Lkcb av tho product llmicrotitanium rlicxidc MT 100 S11 f:-rm the company Tayca, iron oxides anid iron ste-arate, nuch ao, the product "Microtitaniun dioxide MT 100 F"1 from the company Tayca, s ilica,, aluiLii and ,Ulicono, such as the product "'Microtitaniun dioxide MT 100 SAS;" "Micrc'tihanium K dioxide MT 600 SAS" and "MiCrOtiLanium. dioxide MT 50 0 SAS" from the r.nipany Tayca, sodium. eanapopae siich af- the product "'Microtitanium dioxide HT 150 W" fromn Lle company k -U UiHJ~ JJ 1 'if( b6 73 Be le' 12/'81/98 14:'20~? A4 MORKl PY: 9/49, 7 Tayca, oc otyl trime thoxysilanc, such a-is the product "IT-805"' from the company Degrussa, -alumina and st:Eric acid, szc't at- the product 'ItJT- M160" from the coml~pany Kemira, -alumina and cgjycorol, nuc~h the product IEJVT-M212" frout tho company Kemira, -alumina and o i I lecone, such ao. thn product IIJVT-M2 62 1 from the company Hentira.

Th c ux±.reated titaniim o,:ide! may, for ex~ample, be thosc' sold by the company Tayca under the trade xnazes "Microtitanium dioxide MT 500 BII or "Mcrotitaiu diioxide MT 600 1111.

The titanium oxide ninopigment(s) may be prC.SCnt iXn U10 (OcnhtpoSJtiOn CkCC:C)Td1Iii to the invention in a proportion olbetween 1 avd 3O1W, by weight relative to the total weic(rhit of the coxnpo.;Aion, preferably between 2 and 2Y1t, by weight rcJluf..iv( to the total woight of the coautosition.

By mei-uu; of the inVC1.TtA0o, it is possible, without any probA em, to introdtice, relatively large 4 U, amiounts of TiDO,, i~n particular ;wnouxts greater than by weight, Or eV1'ai greater thanT 10", by weight or, oven further, greater Ltan 1556 by weighL., without being penalized by tbh: crbesOf Sty.TI( power in water, photoblueing and whitening mcint'ionnnd above.

one of the essential characteristics of the compositions acccording to the invention is the presence Ar 01301 'g8 Trm NT-i~ FAX 6r. s par: DPI L OREAL 33 1 47 56 73 88 19/Ie~12"8 1 BTiIflP 1B49 of defornable hollw particles of nri expanded copolymer of vinylidene cAhl.w:ido and acrynTlit.rile or of vinylidene chlridn, acrylonitrile and metbacrylate.

The term "deformiiLble" should be undtrrstood hore to mean that the particlp arc flexible and euastic! aftcr crushing, they te.:ume their initia] shape.

These h[2ll.ow particles gc-ne;Cl1y have a particle size raicliniy from 1 aum to 250 jim. These particles advantarjcoeu.sly have a part-icle !ize of less than 100 pm. The ;cat.crn for thi:; in that the finer the particler are, thie nfter the compuition is On application. The particlen- prefeczahiy have a particle size ranging fron 10 1m to 60 pm, The par.t .cles advantageoim:; y have a density ranging from 3- 5kq/m:I to 200 k/mi and, better still, 3 E ~greater~ than 40 kqc/m 3 and/or thlan 100 k~g/cm- and, in particular, ra.Aiiing from 60 kg/in' to 80 kg/r 3 It is Pmsi.., for example, Lo use a copolymer containing: from 1% te 601- of units derived from vinylidene cilur:ide, from 7.0% to 90% of units derived from acryloniirile and Lrmumw 1% to 50% of units derived from an ;w:iylic monomer, Lli sum of the percentages (by wci.qht) being er.qual to 100. The acrylic monomer is, for ecmpJe, a methyl ac.:rylLe or moethacrylate and., ini particular, 1.1w inethacrylate.

The particles are, in partieuthr, in the dry or hydratodc form.

Thin, Jsplye i n-Loyic =6d non-irritant ~Thi- YXL: FAX 6m'is Par: DPI L OHEAL +33. 47 56 7388 16 1281/~98~'42 4H~ g1'l 9 to the skin.

Tile p;ir-tic.-1es are preferzibly in the form of micros~pheres.

The prtrLicles of the invention may be obtained, for exaiiple., a(,cording t~o tile processes of the patents and patent*. appliczitiort- JLP-56,2.19, EP-348,372, EP-48G,080, EI-320,47*3, EV-ll2,607 and US-3, 615,972.

The iiit.erial cavity of ILhe particles~ contains in principle a qjas which may he air, nitrogen or a hydrocarbon such ar, isobutano or iseopcritanc.A Hollow particles which can be used in the invention are, in particular, tlio!;e sold under the brand name ExpaiceJ. by tho company Nobel Casco, such a.,7 Expancel, 551 TE 20 with a particle 4.ive of 30 /inn and a density of 65 k~j/mn 3 approximately; £Bxpanccl 551 DE with a particc So ':izc! of 40 inn.

In Ulf"t C~OMPO.itiorTS Of t~he, invention, from 0.2% to 3% by weight of parLicv.es, anid better -till from 0.5% to I 51, by weight, is preferably u.3ed relatilrQ to the Lota.1 Weight of the., comapositlon.

In the compositions acc:ording to the invention, t~htc fa.tty phase contains compounds conventionally used in the field of mnanufacturn of 2.S anhydrous cnsnui. ILic compositions, in particular such as oil;-, waxy compn(-undrs, emulsifi'.r; and golling agento.

The I:-.nri oil re fers, to a eoxnpouiid which is liquid at room t:emperature. The Lern wax refers to a V~.AX&~s a'DPI L OREALU +33 1 47 56 73 88 le i2/61/98 14:20 A4 MORM Pg 234" FAX 6m is Par: IDPI L OREAL~ +33 1 47 SG 736 BEI'1le 4'8 42-"_4NR Py: 12/49 compound which is asolid or sub!taitially 0solid at roomn tempera1ture, and who'se meltiS~q pc.j~jnt is generally above 0

C.

oils; which may bie menticancd arc mineral oils (petrolatumi), PIInnt Oils (SWoe(-t AlMOnid oil, macadamia oil, blackcur'r-T11: seed oil) andj synthetic oils such as perhydropqualeno; fatty alcoholn, )cids or ster~s (octyl palmitat.(c, isopropyl lanolait.e, triqflyceride3 including capric/capiryiic ac.id triglycerides); oxyethylenated oi- oxypropylen.:ted fatty erters and ethcro; siliciit -con taiiuing oils (cyclome thi conn, po3.ydimethylsi.loxanos, or PDMS) or fluoro oi~rh;A polyalkylenes. Pral erably, the ollsh arc polyalkylezier, such as polybuttwes or, for oxamp I, the hydrogenatc-d polydecene sold unidnr thi! trade T1,111ie "Silklflo S 366 NP" by Albemarlu.. J::;prcopyi palml tate sold under Liie tradc.

name "Estol :1 5:1'11 by 'Unichcxun may 2i1-o be used.

Waxy (:exupoundJ:: which maiy bu mentioned Eire jojoba oil, parafifin, carnaiilba wax, beeswax and hydrogenated uar;tucr oil. The. wax ii.;Aed is, prnferaibly the hydrogenated cai;tor oil :,old undcor the trade name "Cutina IIR"I by Htenk.el.

Emul3 i e rs which xnoiy lie used are fatty acid esters of polye LhyI ne glycol (PElG), fatty acid etsters of glycerol (gflycer-yl stearate) or fatty acid estera of s'ugar (oit Leaatc) we&I I as th polyoxycthyIle:iot.&d or polyoxypropylexm ted de-rivatives the7:cof, cyclor-nic~th~ conurt: and d.i ineth~icone copolyols, I4 i 1 aR '('TIP no qll;'4 r'rY/ Nnl 91821

I

PAX 6m'is par: DPI L OREAL +33 1 47 56 73 88 le 12/81/98 14:280(64 MORN Pg: 13/d49 anionic vurfactauLs (potassiu~m ox: mocditu alkylphosphate), anrd polyadkoxylt.ed fatty alcobols.

Pro fe2:abiy, polyalkoXy).i t,.ed fatty alcohols are ured, such as oxypropylenatcd I btyl alcohols, oxyethylenatcl Qaprylic alcoliols and oxycthylenated cetyl alcohols.

ox'e exrnif~s.ifier which particularl-y suitable for the cQmpositi ns accordincq to the invention is oxypropyJlenatodr buty) alcohol 14 K) (propylene oxide)j sold under thc Lrctdc nam~e "i1Jror, Flti.id AP" by Amerchol.

Gellixcj agn'nto which mt,-ty bu mientioned 'arc modificd clayre (bentQnes), metal ;;ilts of fatty acids (aluminium steardvtte), fethylene/acryUInte copolymers, Pilicas, polyetHiyIene-, ca).cTm elcntsor ethylcc-.lluloc'.4 The fat.Iy phas.e) preter'ably hais a vizcosity which is suffi cLtcIt to maintain in hianopigqnents stably in disperrion.

The cornpcsition~l: of thje invc.ntion may optionally contuiix organic rsereeninq agents, as well as.

other types of iliorgalnic piqgmerit.

obvlou a person skl led in the art will take care to sclcoct the. optional complemnentary compound nterti orid. abovo and/or the amounts thereof s',ich that the adivantageous properties, and in particular' the. j~ioperLies of red.eLion of the photoblueing D~n(I wh-iteninig ph~inomena, intrinsically associated wi Lli the coxparitiont in accordance with the

FF

0< 13/01 '98 TUE 00:31 [TX/RX NO 9182] q 0C.MK BENTLEY Patent Attorney for andf on behalf of the applicant(s)

FX

6 mis par: DPI L OREAL +33 1. 47 S6 73 88Ia1'V84:8(4NJ :139 anionic stirfact-wiLs (potassiuim or Sodiurn alkylphosphat:e) nd polyalkoxylat.ed faxtt~y alcohols.

Prcfer:ably, polyalkoXyL.Lt'.ed fatty alcohols are umied, suchi as oxypropyilenatcd ibutyl. nlcoholr, oxyethylenatocd cprylic alcohols and oxycthylenated cetyl alcohols, Ox'e emlifier which io; particularly suitable for the composit-ions accordingq to the invention is oxypropylenatcd Ibutyl alcohol 14 PC) (propylene oxide) Gellincj agonrto which maz~y be mentioned arc 1 modified clayrs (bentcones), mretal ;its of fatty acids (aluminium ste .zite) eth~ylenti/acryiUait~e copolymers, silicas, polyethyienoo, calciiim Lilcates- or ethylccllulos'..

The fzIl.l.y phatco prettrab.ly h-an a viscosity which is suff 3 c.-L&ent to maintaia thr, namopigments stably in disperrion.

The.- compoition.s- of the invention may optionally conta,.in or-ganic screeninq agents, as well as other types of iiiorganic pigment.

Obvicousjy, a person skilled in the art will take care to scoct the. optional complementary compound(s) menti oned abovo and/or the amounts thereof 2S su-ch that the idvantageous properL-ing, and in particula,,r thec, pro(-pcT.Lies of redu(:tLion of the photoblueiniq and whitenTixig pheiiomiema, intrinsically associated wi LII the compco!;itiozn in accordance with the ~RA 'LVT ~13/01 '98 TUE 00:31 [TX/RX NO 91821 I ILrN" X IA 'T 9' XtA T W A d"XI In 12flD'I

I

U I I FAX 6mis par: DPI L OREAL +33 1 47 S6 73 88

L

Ic 12/01/98 14:20~ M4-HORfl Pg: 14V49 invention arc not., or are substau.Lially not, altered by the addition(.-;) iL~q The compsitions accordling Lo the invention are preferably ijn form of: an anhydrous cream.

The cocittpositiono accordiitq to the invention generally h.a.vfe a s~un protection factor of at least 4, preforably of at,. least 1.0, and evcon more preferably of at least 20, the~ sun protection2 factor (SPF) being expreoved niatheiii~tLicalLy by the rat.io of the irradiation. timo recruired to reach thc! erytheutatogenic threphold with Llie UV ;.creenincj i~t.nt to the time required to tho erythexnatuqtliC threr~hold without a UV screening! ot:"mnt.

Corncrr-hn, but in nio way 1.im:i Ling, examples; illstr .in thi- invention will. now bo given.

.FXAMPLE 1: Comnparative tests wev'! pc.-rfonnecd in order to dcmonstrate tho jiuprovcmcort, affordod by the use of deformable hoJllow aicro~spheres of: an exparndcd copolymer of vinylidene chloride and acrylonitrile or of vinylidene chloride, acrylonitrilo. and methacrylate, in an anhydrous a n tAiun composiLlon containing TiO,..

For an anhydrousr cream containing a certain percciLL,:pJ,- x of Expanc..1 and 20% titanium oxide was prepared iri ;i vfzhicle vaomput~c. of a polyalkoxylated fatty alcohol (oxypropylnated butyl alcohol), a fa.t from the clite~r .f..mily (,ii~opropyl. -p;:lmita te) a wax 13/01. '98 TUB 00:31 [TX/RX NO 9182]

K

A

I

FAX 6r g: 1ar5/49 Pa:DI L OREAL, +33 1 47 SG 73 88 le 12/01/98'14 "20"'64 THORtI :54 13 whosc meltingj pciit is between 60O-and BOOC (hydrogonated ca,;Lor oil), a thirkconinq fat (glycery.

monostearate) and an oil (hydrcogeriated polydecene).

F~.ve cli Ef erent creamns A, B, C, D and E were prepared, varyinti1 Lheu content from 0 to 2%.

Forthe five creams, tue fphotoblueing was evaluated according t~o the fol?.owing~ procedure. The compositions wor<: -introduced into UV-transparent plastic boxes Y,;l-a 1 polystyrene boxes 5O0x4Ox6 cm3) and exposed to UV rayL; (Hraeue, Suntest CPS) for lh.I colorimetric mconutrernteriL! were takt-n using a Minolta CIOOG colorint.vc:. A first measu:cnnvnt war, taken lut 4 before exposurec L Lhe UV rays (TO) and a second afte-r onc hour of cxpo:;Lir~t to the UV rayr, (T3.h) The ro'mc1t.n arv' expreuj-ned in. the L, a, b rystcm in which T, represents the luminance, a represents thce,'Iq~~ axis green, +a red) and b reproscntf; ith, yellow-blue x.Us blue, +b yellow).

In ordf.-v tc evaluate the photoblueing, the values of intcro.ct. are Ab, which iniasures the variation in blue colour, AI,, which measures the blackening of the composition, ,.tnd AB, which c:ue. the variation itotal colour.Mr precisely, Ab and nL are~ defined by 8b= bTJh a.11 d AL= LTm L 1 0 The lower the Ab, the higher thecfl !IlePctivEness of thr. protection against I photobl.uing.

iE ciJculaced from thn -uariations 8L, Aa 13/01 '98 TUE 00:31 [TX/RX'NO 91821 SFA~X nrrI n pa r DP I L, OREAL, +33 1 47 Sc, 73 8 le 12/01/98 14:28 A4 NORMl Pg: 16/49 and Ab Accordinqg Loz the following formula;

(A~

2 (b 2 In Order to evaluate the whitening, teoto were performed on five model~s. '1'hro intens:ity of the whitening (1b) measured on i a ~ele gruded from 0 to The value 0 currospondf, U) a composition. which whitens considerably whereas,- the value 5 corresponds to a composition whic~h qivnp vcry liLLle whitening.

The rcsi1t;art, given in Table below:

I

Table (T) AL7-1.

x 0 lb 2 10.7 .11 1 3 .6 012 60 4.5 95 2.8 3.150 1*1 f .z 0 2.8 2 4.6 2.75 0.95 0.i'1 4.80 -1 2.80 3.7 3.7 These; rou1l t -,how clearly that the introduction of dc(,formab1- hoillow .Wi~roepheres of an expanded co~palynocz f viniylidene chloride and aezloitreo3. o1jvz lde~ chloride, acrylonitrile A'Vr O 13/01, '98 TUE.00:31 [TX/RX laccount ofV 11 y4 phi3i n;vaLu4t T10y, Lerld LCI bd rodi' e ,jo by Water uir~ ~th~~

A

rfrY/RX NO 9182] FAX 4M i E Pr:' DP 1 1 OREALi 33 1 47 SG 73 88 Ia c12/01/98 "14':28" fl, t4"HOJhfPg 17/'149 and methacrylate in an anhydrou- c.r-eanm containing a titanium oxide nicgnif iantly reduces the. photobluning due to the prnsnco of the said titanium oxido, an well an the whitenincL of the compositiori when it is applied to the skin.

Morcovcwvl, compositions 11 to E, in accordance with the invention, proved Lo be very stable.

EXA1PLE 2: The following compo.it..icti giver, a concrete example of a hi1-protection, ;nhylrous antisun cream in accordaincc w!LhL the invention. The amounts art, oxresrnn a6 a by weight relati.vo to the total weight of the composiict: Phase A: oxypropyleritcid Lutyl alcohol 1' PO sold under the trade )iimo "Llcon Fluiid AP'" by Amerchol (emulsifier) i,-opropyl palmi t:ate sold under LUje trade name "Estol 1517" by lricchema hydrogenated ca.ttor oil sold uriIco the trade name "Cutina HRI" by Henkel glyccryl moniltoarate sold under the trade na-me "Tegin 90" by Gol.dschmidt.

12% 12% 7.5% 0.25%

I

1 4 i At

R

i 4 !1 >4 nved, Thus, 'It) Cn~jd~k~rr r(jf1~c conducted WA4 w FrtXs 1 6MI, par: DPI L OREAL +33 147 S6 73 Se 9 1 M A4: ISRI ~49 Phase B; titanim oxido :acA under the trade name "fMT 1OO0V by he magneviLum *ilicte sold undcer the trade name "Talc Luzenac. 15i MOO"1 by Luzonac expanided micy-cm:phcres of vinylidene chloride/ -Acry"-onitrile/motLhyl methacrylato 'iopolymer containing isobuLane, ioold undcir Lho trade name OlExpance. 551 )PR" by Nobel Ca,;Lo hydrogenated polydecene (MW B349) old undor the trade name! 11W;lkfic, S .366 NIM" by

SP.

Albemarle qS lO00' Thio uva wasi prepared in the follow~ng way: phase A was heateud to 901C in urdwi, Lo homQqcni7zc it.

The pigmentary pas:te was then prepared hy mixin the titanium oxide w11.1h the hydroenwat.uci pcAlydccec. The talc and then thtw Expancel were., addttd to this nixture.

The pha.4a B tbuti proparod was heate-d to 90 0 C. The two phases A and 13 were then mixed toge.:ther with a Rayncri nuLxc-r. once the mixture had set, it was again heated to The mixturce was then turbo-mnixed with a Turrax mixer for 10 mintil.&r~i. Tbe creari wa; Lhcn allowed to cool to room Lempocraiir~i with st:irring using a Rayneri mixer.

ThiF, Cvr(a~L hae) a suri p,)roI..-ction factor of is very weakly sutjt-L't. to photLo1uLrng and virtuall~y doc:3 not whiten 0. all when applici Lo the skin.

It is mor~eover very stable.

13/01 '98 TUE 00:31 [TX/RX NO 9182] U. I e-Ar~ All of 9o VL n i vy loQw, or cvven iUoil~inxt.

I chemia ,i3Ajontj a~lso bave the 16A this specification and the claims, the words "comprise", "comprises" and "comprising" are used in a nonexclusive sense.

V

Vt, V v Vt I

I

(III

I V I' V V V VI

(I

r I. I

V

VV

V VI V I V Ia a.

1~ 1 r j It\Simeona\ Keep\ 61296 06 .doc 22/06 /9 8

Claims

1. Anhydrous coome.tic: coxposition, C.hArnctez'ized ill .lhat., it. compr.ser,, i~n a copmetica~ly acceptable vehicl.', consistinq i~ ratty phase, at leapt one titaniuti oxide nanopig't-. rind deformable hollow microophnrs of an expanded cpolymer of VinyXldene cJ o;Jidu and acrylonitrile or of vinylidenc chloride, acryloni trile and W-tha !Vy)atC.

2. Composition acccordiing to Claim 1, characterized in that the microsphoren ho vn a1 particle size ranging from I p~m to 250 ym.

3. Coutpcition accorclngq to Claim characterized in Lhat the micronTphur.) havc a particle size of leav. Lh;-iz 100 12m. 154, Coinposition according to Claim 3, characterized in Lhat the uticrot;phtuzeo ha-ve a partic si.ze ranging from 3.0 p~m to 60 pm. Comnpo.-, it7 on acceerding to any one of the preceding cla±im.~ characteriznd in t-hat the zicrospherers have! a density rurcjin~j from 15 kg/nv to 200

6. Composition accordiiig to Claim characterized in~ that the mijerospheres have a density ranging from 40 kR/mO to 100 ky/n

7. C -oition accovdiuy to any one of the preceding claims. characterizLed in 1.hat the titaniin oxide nanopi.gnieflt. fromn 1it'aiiium oxideo .4treated with7 alwnilna, 'Silica, aI]urninliuin compoinds;, 13/01 '98 TUE 00:31 [TX/RX NO 9182] SA~S" from th(uA company Taya, sodiuml heai .pqp~ Iu~h nn the product "Micoianu hlioide M1T 3.50 VIII From Lhe company t44~ A 1FAlX lknis liar: IDPI TOREAL, +33 1 47 66 73 88 le 12/01/98 14:2 Al4 NORMI Pq: 20/49 silicon compouidht, sodiuim compoundj-., iron oxides, iron esters, stearic acid ancl qlycrycl.

8. '-oipositat-n accordiaq to any one of the preceding claims, c),aracteried. ift Uhat the, microspheres represent from 0.1% to 3% of the total weight of the composition.

9. C.omposition accordingr to Claim 8, characterized in that the microspheres represent from to of the total weiqht of the composition.

10. Composition according to any one of the preceding claims, charactrriznod in that the titanium oxide nanopigc .nt.0 i)jr,(aro) Irt~n thc composition in a proportion cof between I and 30% by weight relative to the total weight± of the composition.

11. Compoition aCCor.TICl to Claim characterized in that the titanium oxide nanopigment (s) prconnt i ii thr, composition ini a proportion of between 2 and 25ll by weight rclot-ivn to the total weight of the compou.ion.

12. Ccnpo;ition according Lo Claim 11, characterized in khttho tiLItaiumT coxldc nanopigment(s) is(are) presont in Lbe-. comnpositioni in a proportion of at least 5% by wi.~rhlt relative to thco total weight of thc composition.

13. Composition accardiriq Lo Claim 12, characterized in fIhat the titanium oxide nanopigment(o) is (iarc) pre.-:ent Lj, the composition i.n a proportion of at least 109t biy wriIht' relat -ve!to Lho total weight of V K A one of the 1 sC3t.nibal clia7.cteristics of the 1 composition accordin o the invention is the presence 13/01 '98 'rr n olf i T v -j the composition.

14. Composition according to Claim 13, characterized in that the titanium oxide nanopigment(s) is(are) present in the composition' in a proportion of at least 15% by weight relative to the total weight of the composition. Composition according to any one of the preceding claims, characterized in that the said fatty phase has a viscosity which is sufficient to maintain the said nanopigments stably in dispersion.

16. Composition according to any one of the preceding claims, characterized in that the said fatty phase comprises at least one oil chosen from mineral oils (petrolatum), plant oils (sweet almond oil, macadamia oil, blackcurrant seed oil) and synthetic oils such as perhydrosqualene; fatty alcohols, acids or esters (octyl palmitate, isopropyl lanolate, triglycerides including capric/caprylic acid triglycerides); oxyethylenated or oxypropylenated fatty esters and ethers; silicone-containing oils S(cyclomethicone, polydimethylsiloxanes or PDMS) or fluoro oils; polyalkylenes.

17. Composition according to any one of the {preceding claims, characterized in that the said fatty phase comprises at least one wax chosen from jojoba oil, paraffin, carnauba wax, beeswax and hydrogenated castor oil. i Thesre particles ri!, in particular, in the dry or hydratod fornm. ThIn .opuclynnrx !r in noL-Lobic and non-irritant /iL L 20

18. A composition as defined in any one of Claims 1 to 17 when used as a cosmetic composition for protecting the skin and/or the hair from the effects of ultraviolet radiation.

19. A composition as defined in any one of claims 1.to 17 when used in the manufacture of a cosmetic composition suitable for protecting the skin and/or the hair from the effects of ultraviolet radiation. Cosmetic treatment process for the photoprotection of the skin or the hair, which consists in applying an effective amount of a composition defined in one of Claims 1 to 17 to the skin or the hair. ci IC I t c I. C C IECCf Dated this 22nd day of June 1998 L'OREAL 25 By their Patent Attorneys GRIFFITH HACK Fellows Institute of Patent Attorneys of Australia I' 1 1 1 1 IC C It C I (I I CS. 4, C V H:\Simeona\Keep\61296 96.doc 22/06/98 Th. :0'r oil ra'ters toc a couipouiid which. is lic~U~d at r'oom temperature. Thr. Lex~n wax rcfers to a .4 I- :FAX'6ind par: DPI L OREAL +33 1 47 56 73 88 le 12/81/98 14:28 A4 NORMj Pg: 2349'~ 2). ANHIMROUS COSMETXC COMJOSITIONS CONTAINING TiO 2 NANOPICMJRNTS AND DEFIORK"ALE HOLLOW MICROSPIEERES The. Prosent invention rclatcf,- to a novel anhydrous Icomposition for topical use which is intended more particular~y for the phot~oprvteiction of the skin and/or th&- hair acainst. ultraviolet. radiation, as well as to its use in fUho c.osmetics field. Thio COmIposition contains, in a cosmctically acceptable vehicle consisting of a tty phase, at lea.z;t onc titanium oxide nanopinen.. aind deformable holl)ow xnicrospheres o~f an expanded copol~ymer of vinylichenn chloride and acrylonitrila or of vinylidene chlcirido, acrylonitrile and methacry.at.o. I I lnl I up rrim, -I pVolyoxyr,, t14y1,-.A~ o y~pp1Af dnrivatives1 ttte~coof, cycl iioh~iconri atnd di ;nthlconc copolyoir,, T V. 1 1/n, I 'R w!il7 nn!l~ ii fTY/P NO 9t821 INTERNATIONAL SEARCH REPORT Intel 'nal Application No PCT/FR 96/00922 A. CLASSIFICATION OPSUDJECI' MATTER IPC 6 A61K7/42 A61K7f48 According to International Patent Classification (IPC) or to both national classification and IPC B. FIELDS SEARCHED Minimum documentation searched (classification system followed by classification symbols) IPC 6 A61K Documentation searched oilier than minimum documentation to the extent that such documents arc included in the fields searched Electronic data base consulted during the international search (name of data base and, whcrc practical, search terms used) C. DOCUMENTS CONSIDERED TO lBE RELEVANT Category Citation of document, with indication, where appropriate, of the relevant passges Relevant to claim No. A *WO,A,92 21315 (LOREAL) 10 December 1992 1 Abstract* *Claims* A WO,A,92 13517 (SUN SMART, INC.) 20 August1 1992 *Abstract* A EP,A,O 523 294 (TAYCA CORPORATION) 201 January 1993 *Abstract A FR,A,2 622 441 (L'OREAL) 5 May 19891 *Abstract A FR,A,2 622 440 (LOREAL) 5 May 19891 *Abstract* MV Further documents are listed in the continuation of box C. IKI Patent family members are listed in annex. *Special categories of cited documents: rT later documencrt published after the international filing date *A dcumnt efiingthegenralstae oftheartwhih i no orprintydate and not in conflict with the application but ''dcnrto ef pth eevac e fte toe un hc i oderstand the principle or theory underlying the consderd tobe f patcuar rlevnceinvention 'E earlier document but published on or after the international document of particular relevance; the claimed invention filig date cannot be considered novel or cannot be considered to L' document which may throw doubts on priority claimn(s) or involve an inventive step when the document is taken alone which i s cited to establish the publication date of another document of particular relevance; the claimed invention citation or other special reason (as specified) cannot be considered to involve an inventive step when the '0 document referring to an orrl disclosure, use, exhibition or docnt is combined with one or more other such doci. other means mients, such combination being obvious to a person skilled documlent published prior to the ntemnational filing date but in the art. later than the priority date clamed W document member of the same patent family Date of the actual completion of the international search Date of mailing of the internautonal search report 18 July 1996 2 6. 07. 96 Name and mailing address of the ISA Authorized officer European Patent Office, P.B. 5818 Patentlaan 2 NL 2280HV Rijswijk Tel. 31-70) 340-2W4, Tx. 31 651 epo W,Lu tn H

31.70) 340-3016 Lutn Lrenn PCI7ISAnl a (seesad shut.) (July 1992) page 1 of 2 1i- I I assoviat(-,d wl t.h Oic., ccmpr .riition iii acr. cirdancc with the 13/01 '98 TUE 00:31 rTx/RX NO fl1821 INTERNATIONAL SEARCH REPORT Intei nai Applicauon No PCT/FR 96/00922 I.4Cofliufaton) DOCUMENTS CONSIDERED TO BE RELEVANT Category' Citation of document, with indication, where appropriate, or the relevant passags Relevant to clam No. A PATENT ABSTRACTS OF JAPAN vol. 11, no. 18 (C-398) [2465] ,17 January 1987 JP,A,61 194013 (TAISHO PHARMACEUTICAL CO. LTD) see abstract A EP,A,0 056 219 (KEMA NORD AB) 21 July 1982 cited in the application *Abstract A EP,A,0 112 807 (KEMANORD AB) 4 July 1984 cited in the application *Abstract* A EP,A,0 320 473 (CASCO NOBEL AB) 14 June 1989 cited -in the application Abstract A US,A,3 615 972 (DONALD S. MOREHOUSE,JR.) 26 October 1971 cited in the application Abstract L 4 Form PC-r/ISA/2II (continuation Of swind abuat) (Julyr 1992) page 2 of 2 a8souiatt-d wi Lth t-lhc cornPo"ItiozL isi koo-ordance with thro 44 13/01 '98 TUE 00:31 [TX/RX NO 9182] I. INTERNATIONAL SEARCH REPORT Infrmaionon atnt arnly embrsIntl onal Application No Infomaton n pten failymemersPCT/ FR 96/00922 Patent document I Publication IPatent family Publication cited in search report date Imember(s) Udate I WO-A-9221315 10-12-92 FR-A- 2677246 11-12-92 AU-B- 1912692 08-01-93 DE-D- 69201564 06-04-95 DE-T- 69201564 20-07-95 EP-A- 0586484 16-03-94 ES-T- 2068715 16-04-95 JP-T- 6510747 01-12-94 WO-A-9213517 20-08-92 US-A- 5223250 29-06-93 AU-B- 668862 23-05-96 AU-B- 1565692 07-09-92 EP-A- 0585239 09-03-94 JP-T- 6509321 20-10-94 US-A- 5531985 02-07-96 EP-A-0523294 20-01-93 NONE FR-A-2622441 05-05-89 LU-A- 87030 08-05-89 BE-A- 1004752 26-01-93 BE-A- 1003842 30-06-92 CA-A- 1303998 23-06-92 CA-A- 1313824 23-02-93 CH-A- 676928 28-03-91 CH-A- 676927 28-03-91 DE-A- 3836630 11-05-89 DE-A- 3836631 11-05-89 FR-A- 2622440 05-05-89 GB-A,B 2211409 05-07-89 GB-A,B 2211736 12-07-89 JP-A- 1149713 12-06-89 US-A- 5427771 27-06-95 US-A- 5000937 19-03-91 FR-A-2622440 05-05-89 LU-A- 87030 08-05-89 BE-A- 1004752 26-01-93 BE-A- 1003842 30-06-92 CA-A- 1303998 23-06-92 CA-A- 1313824 23-02-93 CH-A- 676928 28-03-91 CH-A- 676927 28-03-91 I4 4 Form PCT/ISA/210 (Patent fan~y annex) (July 1972) page 1 of 2 patty 11conco, c)xypropyrfwarec 4-LvuauJi 1 41 from the wite.r (OldlY 0-140PrOPY1 P;ilmitate) ZI wax 13/01 '98 TUE 00:31 [TX/RX NO 8182] INTERNATIONAL SEARCH REPOR Information on patent family members PCt/Fona Application No PC/R96/00922 I Patent document I Publication IPatent family I Publication cited In search report j date member(s) d date FR-A-2622440 DE-A- 3836630 11-05-89 DE-A- 3836631 11-05-89 FR-A- 2622441 05-05-89 GB-A,B 2211409 05-07-89 GB-A,B 2211736 12-07-89 JP-A- 1149713 12-06-89 US-A- 5427771 27-06-95 US-A- 5000937 19-03-91 EP-A-0056219 21-07-82 SE-B- 439599 24-06-85 CA-A- 1176417 23-10-84 JP-C- 1381690 09-06-87 JP-A- 57137323 24-08-82 JP-B- 59053290 24-12-84 US-A- 4397799 09-08-83 EP-A-0112807 04-07-84 SE-B- 452471 30-11-87 DE-A- 3374276 10-12-87 SE-A- 8206733 27-05-84 US-A- 4513106 23-04-85 EP-A-0320473 14-06-89 JP-A- 1156015 19-06-89 SE-A- 8704389 10-05-89 US-A-3615972 26-10-71 NONE 74 iI 4 ii I >1 L~. Form PCT/ISA/210 (paint (Emily annex) (July 1992) page 2 of 2